Modification of inorganic substrates with polymeric materials has been utilized in a range of applications across numerous scientific disciplines including analytical chemistry, biology, and electronics. (Mansky, P., et. al. Science 1997, 275, 1458-1460; Huang, Z. Langmuir, 1997, 13, 6480-6484. Granick, S. et. al. J. Polym. Sci. B. 2003, 41, 2755-2793.) Inorganic substrates can be coated with polymers or other molecules using a number of currently available methods. One popular, simple method involves the physical adsorbtion of a polymer to a substrate through coating or other deposition techniques. Other methods utilize covalent or ionic bonding between functionality on a polymer, or small molecule, and functionality present on the substrate surface to achieve modification. (Denes, A. R. et. al. J. Appl. Polym. Sci. 2001, 81, 3425-3438). While simple adsorption of polymers to metal substrates has proven successful in many cases, this procedure does not produce mechanically robust coatings with long-term stability. Post-adsorption crosslinking (Dong, B. et. al.; J. Appl. Polym. Sci., 2005, 97, 485-497.) of the polymer coating may increase the toughness and short-term performance of the resulting film, but such crosslinking can also result in cracking and flaking of the polymer films over time, resulting in mechanical failure and a dramatic reduction in film properties. The chemical attachment of functional polymers to a metal substrate introduces a stable, robust linkage between polymer chains and the metal substrate and represents a more desirable scenario for many applications where the long-term stability of the coating is required for optimal performance. (Hara, H. et. al. Adv. Drug Del. Rev. 2006, 58, 377-388.) However, the methodologies to prepare covalent attachment of polymers to metallic and non-metallic substrates has thus far been limited to only a few examples of suitable substrates and complimentary chemical functionalities. Such examples include the near-covalent interaction between gold substrates and thiol-functionalized molecules, covalent bonds formed between silica and alcohol, silyl chloride, or silyl alcohol-functionalized compounds, and covalent bonds formed between hydrogen-functionalized silicon surfaces and alkene-substituted molecules. (Mansky, P., et. al Science 1997, 275, 1458-1460, Pesek, J. J.; Matyska, M. T. Interface Science 1997, 5, 103-117.)
Accordingly, it would be advantageous to provide a method of modifying metal surfaces to provide a metal substrate capable of forming covalent bonds with appropriately functionalized polymers or small molecule derivatives.